Processing thermoplastic resins from cellulose and rosin acids



UN' rEn sure I, Patent ed Apnl, 1947 FBOM- CELLULOSE BOSIN ACIDS Eduard Fdrber, New Haven, Con ndrum to V Inc, a corporation at New Pclyxor Chemical 00., Jersey No Drawing.

3 Claims.

Certain resins have cellulose, cellulose. containing materials, pentosans, pentosan containing materials or mixtures 01 these (with' which lign'in may or may not be present as an additional material) to react with those acids and/or acidic materials which constitute the major parts of rosin (colophony) and tall oil. The method of producing such resins comprises heating to a temperature of at least 800 C. a mixture of a'cellulose containing material with a material selected from the group consisting of (1) the resin acids thatare foundv Application December 6, 1943, Serial No. 513,187

been produced by causing in tall oil,'(2) the mixtures of such acids and the fatty acids that are iound in tall oil, and (311';

rosin, the quantity of said acid materials beinir at least about equal by weight to the quantity istics. and generally speaking they are thermo plastic; that is to say, they soften and iiquefy at elevated temperatures. and remain liquid. above I their melting points even after prolonged heat-- ing. and utter-cooling and solidifying they can be remelted again repeatedly. Forconciseness here- 25 ties of those resins can be reduced, their melting after, I refer to these thermoplastic resins as the resina'indicated" or as the "thermoplastic cel-f lulosic resins; it is to be understood not only that both these terms include only the thermoplastic resins identifled above. but also that each of these terms includes all the thermoplastic resins identified above, that is to say each inor a pentosan-containing material (with or with; out lignin but without cellulose) as well as resins oi the class made from cellulose or cellulose-com.

. taining materials (with or without apentosan and with or without lignlnl I have discovered that the melting points of 0 the resins indicated can be raised materially above theirinitial values. and at the same time their solubilities reduced considerably from their initial Values, without destroying desirable characteristics of these resins. I have discovered also that these resins indicated can be converted into thermosetting resins, and as desired into infusible, substantially insoluble solids, again without destroying their desirable characteristics; in this latter case their melting points are raised to such mixing the resins with relatively small amounts oi hexamethylenetetramine. A reaction Iollows at all ordinary temperatures, although rather slowly with some of the agents, and instead 0! mixing at room temperatures heat may be applied to speed the reaction. or to increase the efiect.

I am aware that hexamethylenetetramine has been used heretofore as a hardening agent for thermosetting resins; that is to say, to increase the hardness oi, for example, phenolic resins which, at elevated temperatures, solidify into more or less iniusible masses regardless of the presence or absence of the hexametbylenetetramine. The action of hexalnethylenetetramine. on the resins indicated however (as well as the actions of the other agents named above) I isouite difierent from the action of hexamethyh enetetramine on the thermosetting resins. In thecase of the latter or phenolic resins, the reagent acts solely to increase the hardness of the ultimate iniusible former the resin. In the case of the resins indicated, the agent constitutes a means, I have discovered, whereby the solubilipoints raised, and (under proper conditions) the resin transformed from a thermoplastic to a titermosettlng resin, all without destroying characable.

Speaking generally, a very small cuantlty of to one hundred parts of the resin is suiilcient.'- The foregoing and all other proportions men-' tioned herein are by weight. The particular prothe kind or grade of resin employed; the eflects oi diflerent proportions vary considerably as appears hereafter.

To illustrate the actions 01 the various agents, I shall describe various applications of them to the resin made by heating a mixture of one part 01' waste paper in finely divided form, one part of rosin, and one-half part of tall oil to a temperag ture of over 300 0., say to about 360 C.,, while an extent, as it were, that the resins become in,

fusible to all practical intents and purposes, .and herein I use the phrase raising the melting point as including producing the iniusibgle str n except as the contrary appears.

allowing the volatile matters to evaporate and be discharged from the mixture. After the completion of the reaction and the removal of the non-resinous 'part oi the residue. the end product to is about one and tour-tenths parts of resin. which teristics which make the resins indicated desirwhen using hexamethylenetetramine, from about I P rtions to be used in any instance depend on the result to be achieved, and to a certain extent on 1 melting point from approximately 120 C. It is to be understood that this resin is used here as representative of all the resins indicated; that is to say, it is referred to herein simply as one example ofthe class of resins to which my present discovery is applicable.

Example 1,-'-Take one hundred parts of the resin'mentionedabove, melt it, and thoroughly mix with it two-tenths' part of hexamethylenetetramine and hold the mixture at from 160 C. to 180C. for thirty minutes. On cooling it will be found that the melting point of the resin is notlceablyhigher than before.

Example 2.--Take one hundred parts of the same resin, melt it, mix with it four-tenths part .of he'xamethylenetetramine, and hold the mixture at about. 175". C. for about ten minutes. By the end of that time the fluid will have become noticeably more viscous, and on cooling the resin will be found to have a melting point noticeably higher than the melting point of the product of Example -1. If the mixture of this Example 2 is held at the same temperature, namely, at about 175 C., for about fifteen minutes, and then cooled until solidified and then again heated, it will be found that the first softening point of the resin is now about 145 C. If the same mixture is held at this temperature, namely at about 175 C., for periods longer than fifteen minutes, it will be found that the melting point of the resin rises as the period of the heating is lengthened until the melting point reaches about 150 C.

The solubilities of the resin decrease as the melting point rises. For example, before the addition of the hexamethylenetetramine the resin dissolves easily in aromatic hydrocarbons of low boiling points. When however the melting point has been raised to about 145 C. by the procedure above, solution of the resin requires larger amounts of thesame solvents, and when the melting point has been raised to above about 145 C., the resin cannot be completely dissolved in those solvents, but only in solvents having higher boilins points. I

Example 3.-With the same materials, proportions and procedure as in Example 2, but holding the mixture at from about 195 C. to about 200 C., the rise in the melting point is achieved in from about two to about five minutes.

Example 4.-Using the same materials, temperatures and procedure as in Examples 2 and 3, butusing six-tenths part of the hexamethylenetetramine instead of four-tenths part, substantially the same changes are brought about in about half thetimes mentioned in Examples 2 and 3.

Example 5.-Take one hundred parts of the described resin, melt it, and mix with it one part of hexamethylenetetramine at a temperature of about 175- C. The liquid becomes highly viscous at this temperature in a few seconds. On cooling it will be'found that the melting point of the resin is now about 170 C. The solubility of this resin is materially less than the solubility following the treatments of the preceding examples,

Example 6.With the same materials, proportions and procedure as in Example 5, except that the mixture is heated'to about 200 C., the' mass solidifies in about two to three minutes. That is to say,-the resin sets at this temperature. It

Example 7.With the same materials, proportions and procedure 'as in Example 5, but heating the mixture to above 200 C., for example to about 210 C., acomplete change occurs in about one-half a minute. The resin then solidifies at this temperature and becomes infusible and substantially or quite insoluble.

Example 8.'Take one hundred parts of the" described resin, melt it, thoroughly Inix'with it one and two-tenths parts of hexamethylenetetramine, and heat to from about 160 C. to about 170 C. The resin solidifies and becomes infusible, and substantially or quite insoluble, in a few seconds.

It thus appears that the addition to the resins indicated, of hexamethylenetetramine in. small quantities, specifically in quantities of from about two-tenths of one per cent to less than two per cent of the resin, by weight, reduces the solubility of those resins, raises their melting points, and in the upper part of the range, and at least with the aid of heat, transforms those thermoplastic resins into thermosetting resins and renders the same quite or substantially insoluble, at least in the commonly encountered solvents. The application or heat hastens the reaction; in longer times however the reaction appears to take place even at ordinary temperatures. The same effect cannot be produced by substituting for the hexamethylenetetramine, formaldehyle in either its monomeric or polymeric forms, or by substituting hydrofurfuramide.

It is to be understood that the-maximum quantities of the agents indicated above, are only the maximum quantities required for the complete reactions. Quantities of the agents greater than the maximum indicated above can be used without changing the results, excepting that (as before indicated) under similar conditions greater quantities bring the reaction to an end more quickly than lesser quantities, and for this reason quantities greater than some of those indicated above may make the operations difllcult to perform, or even may produce non-homogeneous products due to a rapid rise in the viscosity making it difiicult or impossible to mix the components uniformly. Therefore excesses over quantitles of the agents indicated above are only unneeded excesses, and are to be regarded as such for the purposes of this specification. Further, plasticizers can be added to the resin either before or simultaneously with the mixing of the resin and agent or agents as described above, or even subsequently in those instances when the infusible form is not achieved immediately. However, additions of plasticizers tend to reduce the speed of the reactions, and may require the i use of larger quantities of the agents than specihe understood in accordance with the foregoing.

It will be understood, of course, that my inventlon is not limited to the details of the operation nor to the specific examples described above, excent as appears hereafter in the claims.

I claim:

1. The method of changing the qualities of a thermoplastic resin produced by heating to a temperature of at least 300 C. a mixture of a celluloee containing material with a material selected from the group consisting of (1) the resin acids that are found in tall oil, (2) the mixtures or such acids and the fatty acids that are round in tall oil, and (3) rosin, the quantity ot said acid materials beingat least about-equalby weight to the quantity of the cellulose containing substance, which comprises mixing with one hundred parts or the thermoplastic resin, from about two-tenth part to about two parts of hexamethylenetetramine, the proportions being by weight.

2. The method of claim 1, characterized by heatinz the mixture 0! the thermoplastic resin and the hexamethylenetetramine to from about 160 C. to about 220 C.

3. The method of claim 1, characterized by the fact that the resin is melted and the hexameth- French "Ila 23, 1938 

